It is known that isobutylene and other isoalkenes, or iso-olefins, produced by hydrocarbon cracking may be reacted with methanol and other C1-C4 lower aliphatic alcohols, or alkanol, over an acidic catalyst to provide methyl tertiary butyl ether (MTBE) or the like. Generally, it is known that asymmetrical ethers having the formula (CH.sub.3).sub.3 C--O--R, where R is a C1-C4 alkyl radical, are particularly useful as octane improvers for liquid fuels, especially gasoline.
MTBE, ethyl t-butyl ether (ETBE), tert-amyl methyl ether (TAME) and isopropyl t-butyl ether (IPTBE) are known to be high octane ethers. The article by J. D. Chase, et al., Oil and Gas Journal, Apr. 9, 1979, discusses the advantages one can achieve by using such materials to enhance gasoline octane. The octane blending number of MTBE when 10% is added to a base fuel (R+O =91) is about 120. For a fuel with a low motor rating (M+O =83) octane, the blending value of MTBE at the 10% level is about 103. On the other hand, for an (R+O) of 95 octane fuel, the blending value of 10% MTBE is about 114.
The reaction of tertiary olefins with alkanol to produce alkyl tertiary alkyl ether is selective with respect to iso-olefins. Linear olefins are unreactive in the acid catalyzed reaction, even to the extent that it is known that the process can be utilized as a method to separate linear and iso-olefins. The typical feedstream of FCC C.sub.4 or C.sub.4 +crackate used to produce tertiary alkyl ethers in the prior art and containing normal butene and isobutene utilizes only the branched olefin in etherification. This situation presents an exigent challenge to workers in the field to discover a technically and economically practical means to utilize linear olefins, particularly normal butene, in the manufacture of tertiary alkyl ethers.
In recent years, a major development within the petroleum industry has been the discovery of the special catalytic capabilities of a family of zeolite catalyst based upon medium pore size shape selective metallosilicates. Discoveries have been made leading to a series of analogous processes drawn from the catalytic capability of zeolites. Depending upon various conditions of space velocity, temperature and pressure lower oxygenates, such as methanol can be converted in the presence of zeolite type catalyst to olefins which can oligomerize to provide gasoline or distillate or can be converted to produce aromatics or isomerization products. Recognizing the commonality of the feedstock and product between etherification reactions to produce high octane gasoline and zeolite catalyzed conversion reactions, interest has focused on the applicability of combined processes as an approach to advance the art in the production of high octane gasoline.
European Pat. 0026041 to Garwood, incorporated herein by reference, discloses a process for the restructuring of olefins in contact with zeolite catalyst to produce iso-olefins, followed by the conversion of iso-olefins to MTBE and TAME. The restructuring conditions comprise temperature between 204.degree. C. and 315.degree. C. and pressure below 5.1.times.10.sup.4 Pa. In European Pat. 0247802 to Barri et al, it is taught that linear olefins can be restructured in contact with zeolite catalyst, including ZSM-23, to produce branched olefins. The restructuring conditions comprise temperature between 200.degree.-550.degree. C., pressure between 100 and 1000 MPa and WHSV between 1 and 100. It is taught that in the process 1-butene conversion exceeds 59 mole % with a selectivity to isobutene greater than 52 mole %.
It has been discovered that under certain conditions substantial improvements in the art of alkyl tert-alkyl ether production can be realized in a combination or integration of etherification and hydrocarbon conversion processes based upon zeolite type catalysis. In U. S. Pat. Nos. 4,788,365, 4,826,507 and 4,854,939 to M. N. Harandi and H. Owen novel processes are described for carrying out the production of MTBE and TAME wherein unreacted alcohol and light olefin components from the etherification reaction are converted to higher hydrocarbons in contact with zeolite catalyst. These patents are incorporated herein by reference. In these processes the etherification reaction is carried out using C.sub.4 + hydrocarbon feedstream rich subsequent oligomerization of unreacted light olefins.
U.S. Pat. No. 4,605,787 to Chu et al., incorporated herein by reference, describes a process for the preparation of methyl tertiary butyl ether which comprises reacting isobutylene and methanol in the vapor phase in the presence of zeolite catalyst. Under the conditions described for the vapor phase etherification, side reactions, particularly the dimerization of isobutylene, are virtually eliminated. The reaction products are essentially MTBE and unreacted methanol and/or isobutylene.
It is an object of the present invention to provide a process for the etherification of linear olefins, particularly n-butene, to alkyl tertiary alkyl ether, particularly MTBE.
It is another object of the invention to provide a process for the isomerization of linear olefins to iso-olefins followed by the etherification of the iso-olefins so formed to provide alkyl tert-alkyl ethers.
Yet another object of the instant invention is to provide an integrated process for the etherification of linear and branched olefin components of a hydrocarbon feedstream by combining sequential etherification reactions with linear olefin isomerization to produce alkyl tert-alkyl ether, particularly MTBE.
A further object of the present invention is to carry out the foregoing objectives in a technologically practical and economically advantageous process configuration.